KR101809899B1 - Pyridine derivative compound and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a pyridine derivative represented by the following formula (1) and an organic electroluminescent device including the same, wherein the pyridine derivative compound according to the present invention is a compound having high triplet energy (T1) and high thermal stability, The organic electroluminescent device including the same is stable and excellent in light emission characteristics such as luminance, color purity and long life.
[Chemical Formula 1]

Description

[0001] The present invention relates to a pyridine derivative compound and an organic electroluminescent device including the same,

The present invention relates to a pyridine compound and an organic electroluminescent device including the same, and more particularly, to a pyridine compound having a low driving voltage and excellent in light emission characteristics such as brightness, color purity and long life, and an organic electroluminescent device including the same .

In recent years, the demand for a flat display device having a small space occupation has been increasing due to the enlargement of a display device. The liquid crystal display, which is a typical flat display device, has an advantage of being lighter than a conventional CRT (cathode ray tube) angle is limited and a back light is necessarily required. On the other hand, an organic light emitting diode (OLED), which is a new flat display device, is a display using a self-luminous phenomenon, has a large viewing angle, is slimmer and smaller than a liquid crystal display, And in recent years, application to a full-color display or illumination is expected.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of the organic electroluminescent device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When it falls back to the ground state, the light comes out. Such an organic electroluminescent device is known to have properties such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic electroluminescent device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, light of a desired wavelength can be obtained depending on the type of dopant used.

In order for the organic electroluminescent device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic electroluminescence device has not been sufficiently developed yet. Therefore, there is a continuing need in the art for the development of new materials.

Therefore, the first problem to be solved by the present invention is to provide a long-life pyridine derivative compound having excellent luminance and color purity of green phosphorescence.

A second object of the present invention is to provide an organic electroluminescent device comprising the pyridine derivative compound.

In order to achieve the first object of the present invention,

There is provided a pyridine derivative represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

R ₁ and R ₂ are each independently a hydrogen atom, a heavy hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 40 carbon atoms, a substituted or unsubstituted amino group having 2 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1- A substituted or unsubstituted C6-C40 cycloalkylene group, a substituted or unsubstituted C1-C20 alkylene Is selected from substituted or unsubstituted germanium group, a substituted or unsubstituted, a substituted or unsubstituted boron,

n is an integer of 2 to 4,

o is an integer from 0 to 5,

When n and o are 2 or more, a plurality of R ₁ and R ₂ may each independently be the same or different.

According to an embodiment of the present invention, each of R ₁ and R ₂ independently represents an aryl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms A halogen atom, an aryloxy group having 6 to 24 carbon atoms, a silyl group having 1 to 24 carbon atoms, hydrogen, and deuterium.

According to another aspect of the present invention,

Anode; Cathode; And a layer containing a pyridine derivative compound represented by the formula (1), interposed between the anode and the cathode.

Since the pyridine derivative represented by Formula 1 according to the present invention is a compound having a high triplet energy (T1) and high thermal stability, the organic electroluminescent device including the pyridine derivative compound is excellent in brightness, color purity, And can be usefully used for display and illumination.

1 is a schematic view of an organic electroluminescent device according to one embodiment of the present invention.
2 is a graph showing TGA and DSC of Formula 12 according to one embodiment of the present invention.
3 is a graph showing TGA and DSC of Formula 29 according to an embodiment of the present invention.
4 is a graph showing EL spectra of [Formula 29] and [Comparative Example 1] according to an embodiment of the present invention.
5 is a schematic diagram showing the structure of a pyridine derivative compound according to the present invention.

Hereinafter, the present invention will be described in more detail.

The pyridine derivative compound according to the present invention is characterized by having a high triplet energy (T1) and a high thermal stability, which are represented by the above formula (1) and are characterized in that various substituents are bonded to the pyridine derivative compound.

In the pyridine compound according to the present invention, the substituents of the above formula (1) will be more specifically described below.

Wherein R ₁ and R ₂ are each independently selected from the group consisting of a deuterium atom, a cyano group, a halogen atom, a hydroxyl group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, An amino group, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, An aryloxy group, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus, and boron, and may be further substituted by such a substituent.

Specific examples of the alkyl group as the substituent used in the present invention include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a heptyl group, A halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (in this case, a " alkylsilyl group "hereinafter), a substituted or unsubstituted amino group _{(-NH 2, -NH (R)} , -N (R ') (R"), where R, R' and R "are independently C 1 each A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, An aryl group having from 5 to 24 carbon atoms, an aryl group having from 5 to 24 carbon atoms, an arylalkyl group having from 6 to 24 carbon atoms, a heteroaryl group having from 3 to 24 carbon atoms, or a heteroarylalkyl group having from 3 to 24 carbon atoms.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, And can be substituted with substituents similar to those in the case of the alkyl group.

Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

Specific examples of the aryl group as the substituent group used in the compound of the present invention include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, Examples of the aryl group include phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, , Anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, tetrahydronaphthyl group and the like, which may be substituted with the same substituents as those in the case of the alkyl group.

Specific examples of the heteroaryl group used as the substituent in the compound of the present invention include pyridinyl, pyrimidinyl, triazinyl, indolinyl, quinolinyl, pyrrolidinyl, piperidinyl, An oxazolyl group, an oxadiazolyl group, a benzoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a triazolyl group, an imidazolyl group, a benzoimidazole group, And at least one of the hydrogen atoms of the heteroaryl group may be substituted with the same substituent as the alkyl group.

In the present invention, the term "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, aryl, arylalkyl, arylalkenyl, heteroaryl, Substituted or unsubstituted with at least one substituent selected from the group consisting of an acetylene group, a nitrile group and an acetylene group.

Although the present invention is not limited by the specific examples of the pyridine derivative compounds according to the above-mentioned formula (1) having the above-mentioned structure, specifically, any one of the compounds represented by the formulas (2) to .

[Chemical Formula 2] < EMI ID =

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

[Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 28] [Chemical Formula 28]

[Chemical Formula 32] [Chemical Formula 32]

[Chemical Formula 35] [Chemical Formula 35]

[Chemical Formula 40] [Chemical Formula 40] [Chemical Formula 40]

[Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62] [Chemical Formula 65] [Chemical Formula 65]

[Chemical Formula 67] [Chemical Formula 68] [Chemical Formula 69]

[Chemical Formula 71] [Chemical Formula 72] [Chemical Formula 73]

[Chemical Formula 75] [Chemical Formula 76] [Chemical Formula 77]

[Formula 79] [Formula 80] [Formula 81]

[Chemical Formula 82]

[Chemical Formula 88] [Chemical Formula 88] [Chemical Formula 89]

[Chemical Formula 91] [Chemical Formula 92] [Chemical Formula 93]

[Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 100] [Chemical Formula 100]

[Formula 103] [Formula 103]

[Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

[Chemical Formula 115]

[Chemical Formula 120] [Chemical Formula 120] [Chemical Formula 120]

[Formula 124] [Formula 124] [Formula 125]

[Formula 126] < EMI ID = 129.1 >

[Formula 130] < EMI ID = 131.0 >

[Formula 135] [Formula 135] [Formula 137]

[Chemical Formula 140] [Chemical Formula 140] [Chemical Formula 140]

[Chemical Formula 144] [Chemical Formula 144] [Chemical Formula 145]

The method for producing the pyridine derivative compound according to the present invention is specifically shown in the following Examples.

The present invention also relates to a fuel cell comprising an anode; Cathode; And a layer containing a pyridine derivative compound represented by the formula (1), interposed between the anode and the cathode.

In this case, the layer containing the pyridine derivative compound is preferably a light emitting layer between the anode and the cathode, and a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer, ≪ RTI ID = 0.0 > and / or < / RTI >

In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 0.5 nm to 500 nm, and the light emitting layer may further include Ir (ppy) ₃ of the following structural formula.

[Ir (ppy) ₃ ]

As a specific example, a hole transport layer (HTL) may be additionally stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic emission layer. An electron donor molecule having a low ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative having a basic skeleton of triphenylamine is used as the hole transport layer. It is widely used.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. For example, N, N'-bis (3-methylphenyl) -N, N'- , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD).

A HIL (Hole Injection Layer) may be additionally deposited on the lower portion of the hole transport layer. The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. For example, (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine), m-MTDATA (4,4', 4" -tris- (3-methylphenylphenylamino) triphenylamine).

In addition, the electron transport layer used in the organic electroluminescent device according to the present invention can transport electrons supplied from the cathode smoothly to the organic luminescent layer and inhibit the movement of holes which are not bonded in the organic luminescent layer, . The material of the electron transport layer is not particularly limited as long as it is commonly used in the art. For example, oxadiazole derivative PBD, BMD, BND or Alq ₃ can be used.

Meanwhile, an electron injection layer (EIL) may be further formed on the electron transport layer to facilitate injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer material As long as it is commonly used in the art, it can be used without any particular limitation. For example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO can be used.

The organic electroluminescent device according to the present invention can be used for a display device, a display device, an element for a single color or a white light, and the like.

1 is a cross-sectional view showing the structure of an organic electroluminescent device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic emission layer 50, an electron transport layer 60 and a cathode 80, The electron injecting layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic electroluminescent device of the present invention and its manufacturing method will be described as follows. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30. A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to another embodiment of the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer is formed by a single molecular deposition method or a solution process And the organic electroluminescent device according to the present invention can be used for a display device, a display device, and a monochromatic or white illumination device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Synthesis Example 1 Synthesis of Compound Represented by Formula 3

(1) Synthesis of Compound Represented by Formula (1-a)

A compound represented by the formula (1-a) was synthesized by the following reaction scheme (1).

[Reaction Scheme 1]

[Chemical Formula 1-a]

165 g (1.05 mol) of 2,2'-bipyridine was added to a 5 L round bottom flask, dissolved in 570 mL of chloroform, and then cooled to -78 ° C. 389 g (2.25 mol) of m-chloroperbenzoic acid was added to dissolve in 1.5 L of chloroform. After stirring at room temperature for 12 hours, the solid was filtered. The solid was washed with methanol and filtered. This process was repeated twice to obtain 172.3 g (yield: 89.4%) of the compound represented by the formula (1-a).

(2) Synthesis of Compound Represented by Formula (1-b)

[Chemical Formula 1-b] was synthesized by the following Reaction Scheme 2.

[Reaction Scheme 2]

[Chemical Formula 1-b]

In a 2 L round bottom flask, 199 g (1.06 mol) of [Formula 1-a] obtained from Reaction Scheme 1 was added and 1038 g (10.58 mol) of oleum sulfuric acid was added and stirred. Fuming nitric acid was slowly added dropwise at a low temperature and stirred at 80 占 폚 for 12 hours. The temperature was lowered to room temperature and slowly poured into 4.5 L of cold water. The resulting solid was filtered and sufficiently washed with water to obtain 126.9 g (yield: 43%) of the compound represented by the formula (1-b).

(3) Synthesis of Compound Represented by Formula (1-c)

The compound represented by the formula (1-c) was synthesized by the following reaction scheme [3].

[Reaction Scheme 3]

[Chemical Formula 1-c]

126 g (0.456 mol) of [Formula 1-b] obtained from Reaction Scheme 2 was added to a 5 L round bottom flask and 1.9 L of acetic acid was added thereto. Then, 140 g (1.14 mol) of acetyl bromide was slowly added dropwise at 40 ° C. After 3 hours, the mixture was cooled to room temperature, and the mixture was neutralized with sodium hydroxide in 19 L of cold water. The solid was washed with methanol and then filtered. This process was repeated twice to obtain 116 g (yield 74%) of a compound represented by the formula [1-c].

(4) Synthesis of a compound represented by the formula (1-d)

[Chemical Formula 1-d] was synthesized by the following Reaction Scheme 4.

[Reaction Scheme 4]

[Chemical formula 1-d]

37 g (0.1 mol) of [Formula 1-c] obtained from Reaction Scheme 3 was placed in a 2 L round bottom flask, and 950 mL of chloroform was added to dissolve the solution. 297 g (1.1 mol) of tribromophosphine was slowly added dropwise at -3 DEG C, followed by stirring at 60 DEG C for two hours. After cooling to room temperature, it was put into 1 L of water and adjusted to pH 11 with caustic soda. After extraction with methylene chloride, the organic layer was separated to remove water, and the solvent was removed by distillation under reduced pressure. The precipitated solid was washed with ethanol and then filtered to obtain 26 g (yield: 77%) of a compound represented by the formula [1-d].

(5) Synthesis of Compound Represented by Formula (1-e)

[Chemical Formula 1-e] was synthesized by the following Reaction Scheme 5.

[Reaction Scheme 5]

[Formula 1-e]

2L round bottom flask into the bromo-nitrobenzene 100g (0.501mol), bis To the solution were dissolved in toluene 1.5L (pinacolato) diboron 150.9g (0.593 mol), Pd ( dppf) Cl 2 12.1g (0.015 mol) of potassium acetate and 145.8 g (1.493 mol) of potassium acetate were added thereto, followed by refluxing for 10 hours. The solution was cooled to room temperature, and the solvent was distilled off under reduced pressure. The resulting solid was separated by column chromatography using n-hexane as eluent to obtain 80 g (yield 65%) of a compound represented by the formula 1-e .

(6) Synthesis of a compound represented by the formula (1-f)

[Chemical Formula 1-f] was synthesized by the following Reaction Scheme 6.

[Reaction Scheme 6]

[Chemical Formula 1-f]

25 g (0.080 mol) of [Formula 1-d] obtained from Reaction Scheme 4, 47.6 g (0.191 mol) of Formula 1-e obtained from Reaction Scheme 5 and 22.1 g (0.160 mol) of potassium carbonate were added to a 500 mL round bottom flask, , Tetraquistriphenylphosphine palladium (4.6 g), water (40 mL), toluene (100 mL) and tetrahydrofuran (100 mL), and the mixture was refluxed for 24 hours. After completion of the reaction, the reaction product was separated into layers, the water layer was removed, and the organic layer was separated, concentrated under reduced pressure, and then separated by column chromatography using hexane and dichloromethane as eluent to obtain a solid. -f] was obtained (yield: 87%).

(7) Synthesis of Compound Represented by Formula (1-g) and Formula (1-h)

[Chemical Formula 1-g] and [Chemical Formula 1-h] were synthesized by the following Reaction Scheme 7.

[Reaction Scheme 7]

[Chemical Formula 1-g] [Chemical Formula 1-h]

13.0 g (0.033 mol) of [Formula 1-f] and 42.7 g (0.163 mol) of triphenylphosphine obtained in Reaction Scheme 6 were dissolved in 200 mL of o-dichlorobenzene and refluxed for 24 hours in a 500 mL round bottom flask. When the reaction is completed, the solution is cooled to room temperature, and the solvent is removed by distillation under reduced pressure. The resulting solid is separated by column chromatography using dichloromethane as a developing solvent to obtain the compound represented by Formula 1-g, (Yield: 54%) and 2.4 g (yield: 22%) of the compound, respectively.

(8) Synthesis of Compound Represented by Formula 3

[Chemical Formula 3] was synthesized by the following Reaction Scheme 8.

[Reaction Scheme 8]

(3)

2.0 g (0.0060 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7, 5.4 g (0.0167 mol) of bromotriphenylamine, 5.9 g (0.0180 mol) of cesium carbonate, 0.7 g (0.0102 mol) of copper, 0.03 g (0.0001 mol) of 18-crown-6 and 30 mL of dichlorobenzene were placed and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then the residue was purified by column chromatography using methylene chloride and hexane as developing solvents. 3.0 g (61.4%) of the compound to be displayed was obtained.

MS: m / z Calcd 820.33; found 820. Anal. Calcd. for C ₅₈ H ₄₀ N ₆ : C, 84.55; H, 4.91; N, 10.24. Found: C, 83.98; H, 4.83; N, 10.11.

&Lt; Synthesis Example 2 > Preparation of a compound represented by the formula (12)

(1) Synthesis of Compound Represented by Formula (2-a)

A compound represented by the formula (2-a) was synthesized by the following reaction scheme [Reaction formula 9].

[Reaction Scheme 9]

[Chemical Formula 2-a]

In a 100 mL round bottom flask, 6.53 g (0.039 mol) of carbazole and 3 g (0.016 mol) of 2,4,6-chloro-1,3,5-triazine were added and 50 mL of nitrobenzene was refluxed for 12 hours. After completion of the reaction, the temperature was lowered to room temperature and the solvent was distilled off under reduced pressure. The residue was recrystallized from dichloromethane and methanol, and the solid was dried to obtain 4.2 g (58.9%) of the compound represented by the formula (2-a).

(2) Synthesis of a compound represented by the formula (2-b)

[Chemical formula 2-b] was synthesized by the following reaction scheme [Reaction formula 10].

[Reaction Scheme 10]

[Formula 2-b]

2.0 g (0.0060 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 1.4 g (0.0066 mol) of iodobenzene, 1.7 g (0.0120 mol) 0.2 g (0.0012 mol) of copper iodide and 20 mL of o-xylene were added thereto and refluxed for 24 hours. After completion of the reaction, o-xylene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using hexane and ethyl acetate as eluent to obtain a solid. (83.1%) was obtained.

(3) Synthesis of Compound Represented by Formula 12

A compound represented by the formula (12) was synthesized by the following reaction scheme (11).

[Reaction Scheme 11]

[Chemical Formula 12]

0.4 g (0.00974 mol) of sodium hydride and 10 mL of N, N-dimethylformamide were added to a 100 mL round bottom flask, and the mixture was stirred at 0 ° C. 2.0 g (0.00487 mol) of the compound represented by the formula 2-b obtained from the above-mentioned scheme 10 was dissolved in 20 mL of dimethylformamide, and the mixture was slowly added dropwise and stirred for 1 hour. 2.6 g (0.005844 mol) of the compound represented by the general formula [2-a] obtained from the above-mentioned scheme [9] was dissolved in 20 ml of dimethylformamide, added dropwise to the reaction solution, and the mixture was stirred for 5 hours. When the reaction was terminated, water was poured to form a solid. The solid was filtered, and dichloromethane and hexane were separated by column chromatography using a developing solvent and recrystallized from dichloromethane and hexane to obtain 1.7 g (42.4%) of a compound represented by the formula (12).

MS: m / z Calcd 819.29; found 819. Anal. Calcd. for C ₅₅ H ₃₃ N ₉ : C, 80.57; H, 4.06; N, 15.37. Found: C, 80.21; H, 3.97; N, 15.61.

&Lt; Synthesis Example 3 > Preparation of a compound represented by the formula (17)

(1) Synthesis of Compound Represented by Formula 3-a

A compound represented by the formulas (3-a) and (3-b) was synthesized by the following scheme (Scheme 12).

[Reaction Scheme 12]

[Formula 3-a] [Formula 3-b]

20.0 g (0.1556 mol) of 4-amino-2-chloropyridine, 27.8 g (0.1711 mol) of iodine chloride, 98.1 g (0.3111 mol) of potassium acetate and 60 mL of acetic acid were placed in a 1 L round bottom flask, Lt; / RTI &gt; The reaction mixture was concentrated under reduced pressure and then recrystallized from methylene chloride and a hexane solvent to obtain 16.0 g (40.4%) of [Formula 3-a] and 18 g (45.5%) of [Formula 3-b].

(2) Synthesis of Compound Represented by Formula 3-c

[Chemical Formula 3-c] was synthesized by the following Reaction Scheme 13.

[Reaction Scheme 13]

[Chemical Formula 3-c]

18.0 g (0.0715 mol) of [Formula 3-b], 12.8 g (0.0679 mol) of 4-bromosuophenol, 0.7 g (0.0036 mol) of copper iodide and 8.9 g (0.1430 mol) of potassium carbonate and 19.8 g (0.1430 mol) of potassium carbonate were added to 180 ml of isopropanol, and the mixture was refluxed for 24 hours. The mixture was cooled to room temperature and then concentrated under reduced pressure. The residue was recrystallized from methylene chloride and a hexane solvent to give 3- (68.1%) was obtained.

(3) Synthesis of Compound Represented by Formula 3-d

[Chemical Formula 3-d] was synthesized by the following Reaction Scheme 14.

[Reaction Scheme 14]

[Chemical formula 3-d]

14.6 g (0.0463 mol) of the compound represented by the formula [3-c] obtained from the reaction scheme 13 and 600 mL of acetone were added to a 1 L round bottom flask, and 4.8 g (0.0463 mol) of butyl nitrite was slowly added thereto. And stirred for 1 hour. 2.1 g (0.0199 mol) of butyl nitrite was added to the reaction mixture, followed by stirring for 2 hours, and water was added slowly to terminate the reaction. The resulting solid was filtered and recrystallized from methylene chloride to obtain 8.0 g (57.9%) of [Formula 3-d].

(4) Synthesis of Compound Represented by Formula 3-e

[Chemical Formula 3-e] was synthesized by the following Reaction Scheme 15.

[Reaction Scheme 15]

[Formula 3-e]

8.0 g (0.0268 mol) of the compound represented by the formula (3-d) obtained from the above-mentioned scheme 14, 12.4 g (0.0616 mol) of bromophenylboronic acid and 1.5 g of tetrakistriphenylphosphine palladium were added to a 200 mL round bottom flask. (0.0513 mol) of potassium carbonate, 50 mL of tetrahydrofuran, 50 mL of dioxane and 20 mL of water were added, and the mixture was refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals. The crystals were recrystallized from methylene chloride and hexane to obtain 7.8 g (58.7%) of [Formula 3-e].

(5) Synthesis of Compound Represented by Formula 17

A compound represented by the formula (17) was synthesized by the following reaction scheme (16).

[Reaction Scheme 16]

[Chemical Formula 17]

2.0 g (0.0060 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 5.5 g (0.0112 mol) of the formula 3-e obtained from the scheme 15 were added to a 100 mL round- 3.3 g (55.1%) of the compound represented by the formula (17) was obtained in the same manner as in the reaction scheme 8].

MS: m / z Calcd 1004.28; found 1004. Anal. Calcd. for C ₆₈ H ₄₀ N ₆ S ₂ : C, 81.25; H, 4.01; N, 8.36; S, 6.38. Found: C, 81.55; H, 4.18; N, 8.19.

&Lt; Synthesis Example 4 > Preparation of a compound represented by the formula (21)

(1) Synthesis of Compound Represented by Formula 4-a

[Chemical Formula 4-a] was synthesized by the following Reaction Scheme 17.

[Reaction Scheme 17]

[Chemical Formula 4-a]

20.0 g (0.0606 mol) of diiodobenzene, 14.8 g (0.0545 mol) of triphenylene-2-boronic acid, 3.5 g (0.00303 mol) of tetrakistriphenylphosphine palladium and 16.7 g mol), tetrahydrofuran (200 mL), dioxane (200 mL) and water (80 mL) were added and refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with methylene chloride and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals. The crystals were recrystallized from methylene chloride and hexane to obtain 15.2 g (65.1%) of a compound represented by the formula 4-a.

(2) Synthesis of Compound Represented by Formula 21

A compound represented by the formula (21) was synthesized by the following scheme (18).

[Reaction Scheme 18]

[Chemical Formula 21]

2.0 g (0.0060 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 4.8 g (0.0112 mol) of the formula 4-a obtained from the scheme [17] were added to a 100 mL round- 2.8 g (51.1%) of the compound represented by the formula (21) was obtained in the same manner as in the reaction scheme 8].

MS: m / z Calcd 938.34; found 938. Anal. Calcd. for C ₇₀ H ₄₂ N ₄ : C, 89.53; H, 4.51; N, 5.97. Found: C, 88.76; H, 4.38; N, 6.09.

&Lt; Synthesis Example 5 > Preparation of a compound represented by the formula (29)

(1) Synthesis of a compound represented by the formula (5-a)

A compound represented by the formula (5-a) was synthesized by the following scheme (Scheme 19).

[Reaction Scheme 19]

[Formula 5-a]

(0.304 mol) of 2-bromoallylene, 81.0 g (0.253 mol) of 2-iodo-9,9-dimethylfluorene, 6.3 g (0.010 mol) of bisdiphenylphosphinobinaphthalene, 4.6 g (0.0051 mol) of bisdibenzylidenacetone palladium, 36.5 g (0.379 mol) of sodium tert-butoxide and 810 ml of dioxane were added and stirred at reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using methylene chloride and hexane to obtain 62.6 g (68%) of the compound represented by the formula 5-a.

(2) Synthesis of Compound Represented by Formula 5-b

[Chemical Formula 5-b] was synthesized by the following Reaction Formula (20).

[Reaction Scheme 20]

[Chemical Formula 5-b]

59.0 g (0.162 mol) of the formula 5-a obtained from the reaction scheme 19, 1.2 g (0.003 mol) of tricyclohexylphosphine tetrafluoroborate, 0.4 g (0.002 mol) of palladium acetate, 44.8 g (0.324 mol) of potassium, 700 mL of N, N-dimethylacetamide, and the mixture was stirred at 130 DEG C for 15 hours. After the temperature was lowered to room temperature and extracted, the organic layer was concentrated under reduced pressure, and then subjected to column chromatography using methylene chloride and hexane to obtain 34.0 g (74.1%) of the compound represented by the formula 5-b.

(3) Synthesis of Compound Represented by Formula 5-c

[Chemical Formula 5-c] was synthesized by the following Reaction Scheme (21).

[Reaction Scheme 21]

[Chemical Formula 5-c]

18.0 g (0.0636 mol) of the compound represented by the formula 5-b], 26.8 g (0.0954 mol) of bromoiodobenzene, 35.2 g (0.254 mol) of potassium carbonate, (0.159 mol) of o-xylene and 348 mL of o-xylene was added thereto, followed by refluxing for 24 hours. After the completion of the reaction, o-xylene was removed by distillation, and the organic layer was separated using water and methylene chloride. The organic layer was separated and concentrated under reduced pressure. The residue was purified by column chromatography using hexane and methylene chloride as eluent to give a solid. 22.1 g (79.2%) of the compound represented by the formula [c] was obtained.

(4) Synthesis of Compound Represented by Formula 29

A compound represented by the formula (29) was synthesized by the following reaction scheme (22).

[Reaction Scheme 22]

[Chemical Formula 29]

2.0 g (0.0060 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme [Reaction formula 7] and 4.9 g (0.0112 mol) of the formula 5-c obtained from the scheme [21] were added to a 100 mL round- 3.0 g (48.5%) of a compound represented by the formula (29) was obtained in the same manner as in the reaction scheme 8].

MS: m / z calcd 1048.43; found 1048. Anal. Calcd. for C ₇₆ H ₅₂ N ₆ : C, 87.00; H, 5.00; N, 8.01. Found: C, 86.25; H, 4.87; N, 8.15.

&Lt; Synthesis Example 6 > Preparation of a compound represented by the formula (52)

(1) Synthesis of Compound Represented by Formula (6-a)

[Chemical Formula 6-a] was synthesized by the following Reaction Scheme 23.

[Reaction Scheme 23]

[Chemical Formula 6-a]

200 g (1.085 mol) of dibenzothiophene and 2 L of chloroform were placed in a 5 L round-bottomed flask and cooled to 0 캜 with stirring. 170.8 g (1.0678 mol) of bromine was dissolved in 512 mL of chloroform and then slowly added dropwise. After completion, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, sodium thiosulfate was extracted with the dissolved water, and the organic layer was collected, concentrated, and then solidified with ethanol. The solid was filtered and recrystallized from methylene chloride and ethanol to obtain 142 g (50.5%) of the compound represented by the formula 6-a.

(2) Synthesis of Compound Represented by Formula 6-b

[Chemical Formula 6-b] was synthesized by the following Reaction Scheme 24.

[Reaction Scheme 24]

[Chemical Formula 6-b]

143 g (0.544 mol) of the compound represented by the above formula [6-a], 152 g (0.598 mol) of bisphenacol diboron and 8.8 g of bisdiphenylphosphinoferrocene dichloropalladium 107g (2.02mol) of potassium acetate, and 1440mL of toluene were placed, and the mixture was refluxed for 6 hours. When the reaction was complete, it was filtered under hot conditions and extracted with toluene and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and separated by column chromatography with methylene chloride and hexane to obtain 161 g (95%) of the compound represented by the formula 6-b.

(3) Synthesis of Compound Represented by Formula 6-c

[Chemical Formula 6-c] was synthesized by the following Reaction Scheme 25.

[Reaction Scheme 25]

[Chemical formula 6-c]

158.4 g (0.51 mol) of the compound represented by the formula 6-b] obtained from the above-mentioned reaction formula [24], 86 g (0.0426 mol) of bromonitrobenzene, 9.8 g of tetrakistriphenylphosphine palladium (0.852 mol) of potassium carbonate, 430 mL of tetrahydrofuran, 430 mL of dioxane, and 172 mL of water were added, and the mixture was refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals. The crystals were recrystallized from methylene chloride and hexane to obtain 62 g (93%) of a compound represented by the formula 6-c.

(4) Synthesis of Compound Represented by Formula 6-d

[Chemical Formula 6-d] was synthesized by the following Reaction Formula 26.

[Reaction Scheme 26]

[Chemical formula 6-d]

200 mL of dichlorobenzene was added to a 500 mL round bottom flask, and after boiling, 20 g (0.0654 mol) of the compound represented by the above formula [6-c] obtained from the above scheme 25 and 42.8 g of triphenylphosphine were added and refluxed for 12 hours. After completion of the reaction, dichlorobenzene was removed by distillation, followed by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 16.6 g (93.1%) of a compound represented by the formula 6-d.

(5) Synthesis of Compound Represented by Formula 6-e

[Chemical Formula 6-e] was synthesized by the following Reaction Scheme 27.

[Reaction Scheme 27]

[Chemical Formula 6-e]

16.0 g (0.0585 mol) of the compound represented by the formula 6-d], 21.2 g (0.0643 mol) of diiodobenzene, 57.2 g (0.1755 mol) of cesium carbonate, 6.3 g g (0.0995 mol), 18-crown-6 (0.312 g, 0.0012 mol) and dichloro benzene (200 mL) were added and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then the residue was purified by column chromatography using methylene chloride and hexane as eluent to obtain a solid. (76.3%) was obtained.

(6) Synthesis of a compound represented by the formula 6-f

[Chemical Formula 6-f] was synthesized by the following Reaction Formula 28.

[Reaction Scheme 28]

[Chemical Formula 6-f]

(0.127 mol) of 3-bromopyridine, 28.0 g (0.139 mol) of 3-bromo-1-phenylboronic acid, 2.9 g (0.0025 mol) of tetrakistriphenylphosphine palladium, (0.254 mol), 200 mL of tetrahydrofuran, and 100 mL of water, and the mixture was refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals, which were recrystallized from ethyl acetate and hexane to obtain 26.5 g (89.1%) of a compound represented by the formula 6-f.

(6) Synthesis of Compound Represented by Formula 6-g

[Chemical Formula 6-g] was synthesized by the following Reaction Scheme 29.

[Reaction Scheme 29]

[Formula 6-g]

2.0 g (0.00598 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 1.3 g (0.00538 mol) of the formula 6-f obtained from the above scheme (28) 5.8 g (0.01794 mol) of cesium, 0.6 g (0.01017 mol) of copper, 0.03 g (0.00012 mol) of 18-crown-6 and 20 mL of dichlorobenzene were added and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation, and the organic layer was separated by using water and ethyl acetate. The organic layer was separated by column chromatography using ethyl acetate and hexane as eluent, and the resulting solid was dried to obtain 6- (69.4%) was obtained.

(7) Synthesis of Compound Represented by Formula 52

A compound represented by the formula (52) was synthesized by the following Reaction Scheme (30).

[Reaction Scheme 30]

(52)

1.8 g (0.00369 mol) of the compound represented by the formula [6-g] obtained from the above scheme [29] and 1.9 g (0.00406 mol) of the [formula 6-e] obtained from the scheme [27] were added to a 100 mL round- 1.6 g (51.9%) of the compound represented by the formula (52) was obtained in the same manner as in the reaction scheme 8].

MS: m / z Calcd 834.26; found 834. Anal. Calcd. for C ₅₇ H ₃₄ N ₆ S: C, 81.99; H, 4.10; N, 10.06; S, 3.84. Found: C, 80.96; H, 3.91; N, 10.84.

Synthesis Example 7 Synthesis of Compound Represented by Formula 65

(1) Synthesis of Compound Represented by Formula 7-a

[Chemical Formula 7-a] was synthesized by the following Reaction Formula 31.

[Reaction Scheme 31]

[Formula 7-a]

To the 500 mL round bottom flask was added 30.0 g (0.3221 mol) of arylene, 61.1 g (0.3866 mol) of 3-bromopyridine, 1.4 g (0.0064 mol) of palladium acetate, 1.3 g (0.00644 mol) of triethylbutylphosphine, 61.9 g (0.6442 mol) of the side, 300 mL of toluene, and refluxed for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 33.1 g (60.5%) of a compound represented by the formula 7-a .

(2) Synthesis of Compound Represented by Formula 7-b

[Chemical Formula 7-b] was synthesized by the following Reaction Formula 32.

[Reaction Scheme 32]

[Formula 7-b]

30.0 g (0.1762 mol) of [Formula 7-a], 25.2 g (0.0801 mol) of 1,3,5-tribromobenzene and 0.8 g (0.0035 mol) of palladium acetate, which were obtained from Reaction Formula 10, were added to a 500 mL round bottom flask, 0.7 g (0.0035 mol) of triethylbutylphosphine, 33.9 g (0.35242 mol) of sodium tert-butoxide, and 300 mL of toluene were placed and refluxed for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted with water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 18.1 g (45.9% .

(3) Synthesis of Compound Represented by Formula 7-c

[Chemical Formula 7-c] was synthesized by the following Reaction Formula 33.

[Reaction Scheme 33]

[Chemical Formula 7-c]

2.0 g (0.00598 mol) of the compound represented by the formula (1-g) obtained from the above-mentioned scheme 7 and 2.7 g (0.00538 mol) of the formula 7-b obtained from the above-mentioned scheme (32) were dissolved in a 50 mL round bottom flask, 5.8 g (0.01794 mol) of cesium, 0.6 g (0.01017 mol) of copper, 0.03 g (0.00012 mol) of 18-crown-6 and 20 mL of dichlorobenzene were added and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation, and the organic layer was separated by using water and ethyl acetate. The organic layer was separated by column chromatography using ethyl acetate and hexane as eluent, and the resulting solid was dried to obtain 6- (43.7%) was obtained.

(4) Synthesis of Compound Represented by Formula 7-d

[Chemical Formula 7-d] was synthesized by the following Reaction Scheme [34].

[Reaction Scheme 34]

[Chemical Formula 7-d]

(0.0844 mol) of 2,6-dibromopyridine, 9.3 g (0.0760 mol) of 3-bromo-1-phenylboronic acid and 2.0 g (0.0017 mol) of tetrakistriphenylphosphine palladium were added to a 500 mL round bottom flask, , Potassium carbonate (23.3 g, 0.1688 mol), tetrahydrofuran (200 mL) and water (100 mL), and the mixture was refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate and concentrated under reduced pressure to obtain crystals, which were recrystallized from ethyl acetate and hexane to obtain 13.6 g (76.2%) of a compound represented by the formula 7-d.

(5) Synthesis of Compound Represented by Formula 65

A compound represented by the following formula (65) was synthesized by the following reaction scheme (35).

[Reaction Scheme 35]

(65)

1.7 g (0.00228 mol) of the compound represented by the formula [7-c] obtained from the above-mentioned reaction scheme 33 and 0.6 g (0.00274 mol) of the [formula 7-d] obtained from the [Reaction scheme 34] were added to a 100 mL round- 1.4 g (70.5%) of the compound represented by the formula (65) was obtained in the same manner as in the reaction scheme 8].

MS: m / z Calcd 900.34; found 900. Anal. Calcd. _{for C 60 H 40 N 10:} C, 79.98; H, 4.47; N, 15.55. Found: C, 79.02; H, 4.35; N, 16.03.

Synthesis Example 8 Synthesis of Compound Represented by Formula 73

(1) Synthesis of Compound Represented by Formula (8-a)

A compound represented by the following formula (8-a) was synthesized by the following reaction scheme (36).

[Reaction Scheme 36]

[Formula 8-a]

20.0 g (0.0813 mol) of 2-bromocarbazole, 19.9 g (0.0975 mol) of bromoiodobenzene, 22.4 g (0.1626 mol) of potassium carbonate, 8.8 g (0.1382 mol) of copper, Was added and refluxed for 24 hours. After completion of the reaction, o-xylene was removed by distillation, and the organic layer was separated by using water and methylene chloride. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using hexane and methylene chloride as developing solvents. 22.4 g (85.6%) of the compound represented by the formula [a] was obtained.

(2) Synthesis of Compound Represented by Formula 73

A compound represented by the formula [Formula 73] was synthesized by the following Reaction Scheme 37.

[Reaction Scheme 37]

(73)

2.0 g (0.0060 mol) of the compound represented by the formula (1-h) obtained from the above-mentioned scheme 7 and 3.6 g (0.0112 mol) of the compound represented by the formula 8-a obtained from the above-mentioned formula (36) were added to a 100 mL round bottom flask ), 2.4 g (49.5%) of the compound represented by the formula (73) was obtained in the same manner as in the reaction scheme [8].

MS: m / z calcd 816.3; found 816. Anal. Calcd. for C ₅₈ H ₃₆ N ₆ : C, 85.27; H, 4.44; N, 10.29. Found: C, 85.89; H, 4.54; N, 10.11.

Synthesis Example 9 Synthesis of Compound Represented by Formula (93)

(1) Synthesis of Compound Represented by Formula 9-a

A compound represented by the following formula [9-a] was synthesized by the following scheme [Reaction formula 38].

[Reaction Scheme 38]

[Chemical Formula 9-a]

16.0 g (0.0585 mol) of the compound represented by the formula [6-d] obtained from the above-mentioned reaction formula 26, 18.2 g (0.0643 mol) of 3-bromo-1-iodobenzene, 57.2 g 6.3 g (0.0995 mol) of copper, 0.3 g (0.0012 mol) of 18-crown-6, and 200 mL of dichlorobenzene were placed and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation, and the organic layer was separated using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then the residue was separated by column chromatography using methylene chloride and hexane as eluent to obtain a solid. (72.5%) was obtained.

(2) Synthesis of Compound Represented by Formula (93)

A compound represented by the formula (93) was synthesized by the following reaction scheme [39].

[Reaction Scheme 39]

&Lt; EMI ID =

2.0 g (0.0060 mol) of the compound represented by the formula (1-h) obtained from the above-mentioned scheme 7 and 4.8 g (0.0112 mol) of the compound represented by the formula 9-a obtained from the above-mentioned scheme 38 were added to a 100 mL round bottom flask ) To obtain 3.3 g (53.1%) of a compound represented by the formula (93) in the same manner as in the reaction scheme [8].

MS: m / z Calcd 1028.28; found 1028. Anal. Calcd. for C ₇₀ H ₄₀ N ₆ S ₂ : C, 81.69; H, 3.92; N, 8.17; S, 6.23. Found: C, 80.88; H, 3.79; N, 8.25.

&Lt; Synthesis Example 10 > Preparation of a compound represented by the formula (112)

(1) Synthesis of Compound Represented by Formula 10-a

A compound represented by the formula [10-a] was synthesized by the following reaction scheme [40].

[Reaction Scheme 40]

[Chemical Formula 10-a]

100.0 g (0.422 mol) of 2,6-dibromopyridine and 200 mL of diethyl ether were placed in a 500 mL round-bottomed flask, and the temperature of the reaction mixture was lowered to -78 ° C under a nitrogen atmosphere. Then, 290 mL of normal butyl lithium mol) was added dropwise for 1 hour. After stirring at the same temperature for 2 hours, 16.1 g (0.106 mol) of phosphoryl chloride was added slowly and stirred at the same temperature for 2 hours. The temperature was raised to room temperature, and the organic layer was separated using water and diethyl ether. The organic layer was concentrated under reduced pressure, and recrystallized from methylene chloride and methanol to obtain 29.0 g (18.9%) of the compound represented by the formula 10-a.

(2) Synthesis of Compound Represented by Formula 10-b

[Chemical Formula 10-b] was synthesized by the following Reaction Formula 41.

[Reaction Scheme 41]

[Chemical Formula 10-b]

29.0 g (0.0923 mol) of the compound represented by the above formula [10-a] obtained from the above-mentioned Reaction Formula 40, 55.2 (0.2217 mol) of the Formula 1-e obtained from the Reaction Scheme 5, 50.9 (0.0036 mol) of tetrakis (triphenylphosphine) palladium, 300 mL of tetrahydrofuran and 150 mL of water were placed, and the mixture was stirred under reflux for 16 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using ethyl acetate and hexane. The solid was dried to obtain 22.5 g (61.3%) of a compound represented by the formula 10-b

(3) Synthesis of Compound Represented by Formula 10-c

The compound represented by the formula (10-c) was synthesized by the following reaction scheme [42].

[Reaction Scheme 42]

[Chemical Formula 10-c]

22.0 g (0.0552 mol) of [Formula 10-b] and 101.4 g (0.3866 mol) of triphenylphosphine obtained in the above Reaction Scheme 41 were dissolved in 280 mL of o-dichlorobenzene in a 500 mL round bottom flask and refluxed for 24 hours . After the reaction was completed, the solution was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by column chromatography using methylene chloride and hexane as eluent to obtain 10.8 g of a compound represented by the formula 10-c (Yield: 58.4%).

(4) Synthesis of Compound Represented by Formula 10-d

[Chemical Formula 10-d] was synthesized by the following Reaction Formula 43.

[Reaction Scheme 43]

[Chemical Formula 10-d]

(0.0319 mol) of bis (trimethylsilylphenyl) amine, 10.8 g (0.0383 mol) of 3-bromo-1-iodobenzene, 0.1 g (0.00064 mol) of palladium acetate, , 6.1 g (0.0638 mol) of sodium tert-butoxide, and 100 mL of toluene, and refluxed for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with water. The organic layer was concentrated under reduced pressure, and then separated by column chromatography using methylene chloride and hexane. The solid was dried to obtain 10.4 g (69.5% .

(5) Synthesis of Compound Represented by Formula 10-e

The compound represented by the formula (10-e) was synthesized by the following scheme (44).

[Reaction Scheme 44]

[Formula 10-e]

2.0 g (0.0060 mol) of the compound represented by the above formula [10-c] obtained from the above-mentioned scheme [42] and 2.5 g (0.0054 mmol) of the compound represented by the above formula [10- 5.9 g (0.0180 mol) of cesium carbonate, 0.7 g (0.0102 mol) of copper, 0.03 g (0.0001 mol) of 18-crown-6 and 20 mL of dichlorobenzene were placed and refluxed for 24 hours. After completion of the reaction, dichlorobenzene was removed by distillation, and the organic layer was separated by using water and ethyl acetate. The organic layer was concentrated under reduced pressure, and then the residue was separated by column chromatography using methylene chloride and hexane as developing solvents to obtain a solid. ] (1.7 g, 43.8%).

(6) Synthesis of a compound represented by the formula (112)

A compound represented by the formula (112) was synthesized by the following scheme (45).

[Reaction Scheme 45]

(112)

2.0 g (0.0060 mol) of the compound represented by the formula [10-e] obtained from the above-mentioned scheme and 3.6 g (0.0072 mol) of bromotriphenylamine were added to a 100 mL round bottom flask in the same manner as in [Reaction formula 8] 4.1 g (70.2%) of the compound represented by the formula (112) was obtained.

MS: m / z Calcd 964.41; found 964. Anal. Calcd. for C ₆₄ H ₅₆ N ₆ Si ₂ : C, 79.63; H, 5.85; N, 8.71; Si, 5.82. Found: C, 80.02; H, 5.99; N, 8.63.

Synthesis Example 11 Synthesis of a compound represented by the formula (134)

(1) Synthesis of Compound Represented by Formula (11-a)

A compound represented by the formula (11-a) was synthesized by the following reaction scheme (46).

[Reaction Scheme 46]

[Formula 11-a]

26.0 g (0.0844 mol) of 1,4-dibromotetraflurobenzene, 9.3 g (0.0760 mol) of 3-pyridylboronic acid, 23.3 g (0.1688 mol) of potassium carbonate, 2.0 g (0.0017 mol) of palladium palladium, 300 mL of tetrahydrofuran and 150 mL of water were added and the mixture was refluxed for 12 hours. When the reaction was completed, it was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and hexane to obtain 16.6 g (71.5%) of the compound represented by the formula (11-a).

(2) Synthesis of Compound Represented by Formula 134

A compound represented by the formula (134) was synthesized by the following reaction scheme (47).

[Reaction Scheme 47]

(134)

2.0 g (0.0060 mol) of the compound represented by the above formula [10-c] obtained from the above-mentioned scheme [42] and 3.4 g (0.0112 mol) of the compound represented by the above formula [11- ) To obtain 3.1 g (54.7%) of a compound represented by the formula (134) in the same manner as in the scheme [Reaction formula 8].

MS: m / z Calcd 949.22; found 949. Anal. Calcd. for C ₅₆ H ₂₇ F ₈ N ₇ : C, 70.81; H, 2.87; F, 16.00; N, 10.32. Found: C, 69.91; H, 2.69; N, 10.72.

&Lt; Examples 1 to 11 > Preparation of Organic Electroluminescent Device

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. DNTPD (700Å) of ITO on the organic material so that after a then attached to a vacuum chamber base pressure was 1 × 10 ^-6 torr substrate, NPD (300Å), the compound + Ir (ppy) ₃ prepared according to the present invention ( Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å).

[DNTPD]

[NPD]

[Ir (ppy) ₃ ]

[Alq ₃ ]

&Lt; Comparative Example 1 &

The organic electroluminescent device for the comparative example was fabricated in the same manner except that CBP of the following structural formula was used in place of the compound prepared by the invention in the device structures of Examples 1 to 11 above.

[CBP]

The organic electroluminescent devices according to Examples 1 to 11 and Comparative Example 1 were measured for the driving voltage, luminance, color index, and longevity, and the results are shown in Table 1 below.

T50 means the time required for the luminance to be reduced to 50% of the initial luminance.

division Host Dopant Doping concentration (%) ETL V Cd / A CIEx CIEy T50 (Hr) Comparative Example 1 CBP Ir (ppy) ₃ 10 Alq ₃ 8.20 38.81 0.29 0.62 76 Example 1 (3) Ir (ppy) ₃ 10 Alq ₃ 5.62 51.11 0.31 0.62 141 Example 2 Formula 12 Ir (ppy) ₃ 10 Alq ₃ 5.34 55.69 0.32 0.63 287 Example 3 Formula 17 Ir (ppy) ₃ 10 Alq ₃ 5.19 50.67 0.32 0.63 113 Example 4 Formula 21 Ir (ppy) ₃ 10 Alq ₃ 4.48 55.71 0.31 0.64 202 Example 5 Formula 29 Ir (ppy) ₃ 10 Alq ₃ 5.11 53.66 0.33 0.62 260 Example 6 Formula 52 Ir (ppy) ₃ 10 Alq ₃ 5.39 49.72 0.31 0.63 174 Example 7 (65) Ir (ppy) ₃ 10 Alq ₃ 5.27 53.90 0.31 0.63 165 Example 8 Formula 73 Ir (ppy) ₃ 10 Alq ₃ 5.09 51.51 0.32 0.64 188 Example 9 Formula 93 Ir (ppy) ₃ 10 Alq ₃ 6.01 49.59 0.32 0.64 168 Example 10 Formula 112 Ir (ppy) ₃ 10 Alq ₃ 4.62 54.01 0.31 0.63 191 Example 11 (134) Ir (ppy) ₃ 10 Alq ₃ 5.21 47.88 0.32 0.63 139

In order to measure the bandgaps of the chemical formula 12, the chemical formula 29 and the chemical formula 112 according to the present invention, the measurement was performed using an absorption spectrophotometer (UV / Vis absorption spectrometer) and a cyclic voltammetry, Are shown in Table 2 below.

division UVl _max PLl _max HOMO (eV) LUMO (eV) Band gap (eV) Formula 12 328 373 6.01 2.68 3.15 Formula 29 330 399 6.04 2.74 3.30 Formula 112 358 401 6.06 2.87 3.19

From the results of Examples 1 to 11, Comparative Examples 1 and Table 1, it can be seen that the compound represented by Formula 1 according to the present invention is superior to CBP, which is a phosphorescent light emitting material, , Luminance, lifetime characteristics, and the like, and thus can be used effectively for display devices, display devices, lighting, and the like.

10: substrate 20: anode
30: Hole injection layer 40: Hole transport layer
50: organic light emitting layer 60: electron transporting layer
70: electron injection layer 80: cathode

Claims (8)

A pyridine derivative represented by any one of the following formulas (1-1) to (1-3)
[Formula 1-1] [Formula 1-2]

[Formula 1-3]

In the above formulas (1-1) to (1-3)
R ₁ and R ₂ are each independently selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms,
Each of R ₁ and R ₂ is independently selected from the group consisting of a deuterium atom, a cyano group, a halogen group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, A heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an aryloxy group having 3 to 40 carbon atoms, An aryl group, and the like. delete The method according to claim 1,
The pyridine derivative represented by any one of the above formulas (1-1) to (1-3) is any one selected from the group consisting of the following formulas (2) to (145) Derivative compounds:
[Chemical Formula 2] &lt; EMI ID =

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

[Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13]

[Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 20] [Chemical Formula 20]

[Chemical Formula 22] [Chemical Formula 23] [Chemical Formula 25]

[Chemical Formula 28] [Chemical Formula 28]

[Chemical Formula 32] [Chemical Formula 32]

[Chemical Formula 35] [Chemical Formula 35]

[Chemical Formula 40] [Chemical Formula 40] [Chemical Formula 40]

[Chemical Formula 43] [Chemical Formula 44] [Chemical Formula 45]

[Chemical Formula 48] [Chemical Formula 48] [Chemical Formula 48]

[Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53]

[Chemical Formula 55] [Chemical Formula 55] [Chemical Formula 55]

[Chemical Formula 60] [Chemical Formula 61]

[Chemical Formula 62] [Chemical Formula 65] [Chemical Formula 65]

[Chemical Formula 67] [Chemical Formula 68] [Chemical Formula 69]

[Chemical Formula 71] [Chemical Formula 72] [Chemical Formula 73]

[Chemical Formula 75] [Chemical Formula 76] [Chemical Formula 77]

[Formula 79] [Formula 80] [Formula 81]

[Chemical Formula 82]

[Chemical Formula 88] [Chemical Formula 88] [Chemical Formula 89]

[Chemical Formula 91] [Chemical Formula 92] [Chemical Formula 93]

[Chemical Formula 95] [Chemical Formula 96] [Chemical Formula 97]

[Chemical Formula 100] [Chemical Formula 100]

[Formula 103] [Formula 103]

[Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10] [Chemical Formula 10]

[Formula 110] [Formula 111] [Formula 112] [Formula 113]

[Chemical Formula 115]

[Chemical Formula 120] [Chemical Formula 120] [Chemical Formula 120]

[Formula 124] [Formula 124] [Formula 125]

[Formula 126] &lt; EMI ID = 129.1 &gt;

[Formula 130] &lt; EMI ID = 131.0 &gt;

[Formula 135] [Formula 135] [Formula 137]

[Chemical Formula 140] [Chemical Formula 140] [Chemical Formula 140]

[Chemical Formula 144] [Chemical Formula 144] [Chemical Formula 145]

Anode;
Cathode; And
And a layer comprising the pyridine derivative compound according to claim 1 interposed between the anode and the cathode. 5. The method of claim 4,
Wherein the pyridine derivative compound is contained in the light emitting layer between the anode and the cathode. 6. The method of claim 5,
And at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, an electron transporting layer and an electron injecting layer is further interposed between the anode and the cathode. The method according to claim 6,
Wherein at least one layer selected from the group consisting of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is formed by a single molecular deposition method or a solution process. 5. The method of claim 4,
Wherein the organic electroluminescent device is used in a display device, a display device, or a device for monochromatic or white illumination.

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